Methods of forming a material layer

ABSTRACT

A method of forming a SiOCN material layer, a material layer stack, a semiconductor device, a method of fabricating a semiconductor device, and a deposition apparatus, the method of forming a SiOCN material layer including providing a substrate; providing a silicon precursor onto the substrate; providing an oxygen reactant onto the substrate; providing a first carbon precursor onto the substrate; providing a second carbon precursor onto the substrate; and providing a nitrogen reactant onto the substrate, wherein the first carbon precursor and the second carbon precursor are different materials.

CROSS-REFERENCE TO RELATED PATENT APPLICATIONS

This is a continuation application based on pending application Ser. No.15/296,220, filed Oct. 18, 2016, the entire contents of which is herebyincorporated by reference. Korean Patent Application No.10-2015-0147540, filed on Oct. 22, 2015, in the Korean IntellectualProperty Office, and entitled: “Material Layer, Semiconductor DeviceIncluding the Same, and Methods of Fabricating the Material Layer andthe Semiconductor Device,” is incorporated by reference herein in itsentirety.

BACKGROUND 1. Field

Embodiments relate to a material layer, a semiconductor device includingthe material layer, and methods of fabricating the material layer andthe semiconductor device.

2. Description of the Related Art

A material used to obtain a minute pattern may be sensitive to hightemperatures, and a low-temperature process may be desirable.

SUMMARY

Embodiments are directed to a material layer, a semiconductor deviceincluding the material layer, and methods of fabricating the materiallayer and the semiconductor device.

The embodiments may be realized by providing a method of forming a SiOCNmaterial layer, the method including providing a substrate; providing asilicon precursor onto the substrate; providing an oxygen reactant ontothe substrate; providing a first carbon precursor onto the substrate;providing a second carbon precursor onto the substrate; and providing anitrogen reactant onto the substrate, wherein the first carbon precursorand the second carbon precursor are different materials.

The first carbon precursor and the second carbon precursor may eachindependently be an alkane having a carbon number of 1 to 10, an alkenehaving a carbon number of 2 to 10, an alkylamine having a carbon numberof 1 to 15, a nitrogen-containing heterocyclic compound having a carbonnumber of 4 to 15, an alkylsilane having a carbon number of 1 to 20, analkoxysilane having a carbon number of 1 to 20, or an alkylsiloxanehaving a carbon number of 1 to 20.

At least one of the first carbon precursor and the second carbonprecursor may include an alkylamine having a carbon number of 1 to 15 ora nitrogen-containing heterocyclic compound having a carbon number of 4to 15; or an alkylsilane having a carbon number of 1 to 20, alkoxysilanehaving a carbon number of 1 to 20, or alkylsiloxane having a carbonnumber of 1 to 20.

The method may be performed at 600° C. or less.

The nitrogen reactant and the second carbon precursor may be the samematerial, and providing the nitrogen reactant and providing the secondcarbon precursor may be performed simultaneously.

Providing the silicon precursor, providing the oxygen reactant,providing the first carbon precursor, and providing the second carbonprecursor may be included in a single cycle.

The first carbon precursor may include an alkane having a carbon numberof 1 to 10, an alkene having a carbon number of 2 to 10, an alkylsilanehaving a carbon number of 1 to 20, an alkoxysilane having a carbonnumber of 1 to 20, or an alkylsiloxane having a carbon number of 1 to20, and the second carbon precursor may include an alkylamine having acarbon number of 1 to 15 or a nitrogen-containing heterocyclic compoundhaving a carbon number of 4 to 15.

The first carbon precursor may include an alkylsilane having a carbonnumber of 1 to 20, an alkoxysilane having a carbon number of 1 to 20, oran alkylsiloxane having a carbon number of 1 to 20.

The silicon precursor and the first carbon precursor may include thesame material, and providing the silicon precursor and providing thefirst carbon precursor may be performed simultaneously.

Providing the first carbon precursor, providing the oxygen reactant, andproviding the second carbon precursor may be included in a single cycle.

The first carbon precursor may include an alkylsilane having a carbonnumber of 1 to 20, an alkoxysilane having a carbon number of 1 to 20, oran alkylsiloxane having a carbon number of 1 to 20, and the secondcarbon precursor may include an alkylamine having a carbon number of 1to 15 or a nitrogen-containing heterocyclic compound having a carbonnumber of 4 to 15.

The method may be performed at 500° C. or less.

The silicon precursor and the second carbon precursor may be the samematerial, and providing the silicon precursor and providing the secondcarbon precursor may be performed simultaneously.

Providing the silicon precursor, providing the oxygen reactant,providing the first carbon precursor, and providing the nitrogenreactant may be included in a single cycle.

The first carbon precursor may include an alkylsilane having a carbonnumber of 1 to 20, an alkoxysilane having a carbon number of 1 to 20, oran alkylsiloxane having a carbon number of 1 to 20, and the secondcarbon precursor may include an alkane having a carbon number of 1 to10, an alkene having a carbon number of 2 to 10, an alkylamine having acarbon number of 1 to 15, or a nitrogen-containing heterocyclic compoundhaving a carbon number of 4 to 15.

The embodiments may be realized by providing a material layer stackincluding a semiconductor substrate; and a SiOCN material layer formedover the semiconductor substrate, wherein the SiOCN material layerincludes about 10 atom % to about 30 atom % of carbon, and about 25 atom% to about 50 atom % of oxygen.

The SiOCN material layer may include about 11 atom % to about 20 atom %of carbon.

The SiOCN material layer may include about 30 atom % to about 48 atom %of oxygen.

A dielectric constant of the SiOCN material layer may be greater than orequal to 1 and less than 5.0.

The dielectric constant of the SiOCN material layer may be greater thanor equal to 1 and less than 4.8.

The dielectric constant of the SiOCN material layer may be greater thanor equal to 1 and less than 4.4.

The material layer stack may further include a SiO₂ layer between thesemiconductor substrate and the SiOCN material layer.

The embodiments may be realized by providing a semiconductor deviceincluding a semiconductor substrate; an isolation layer defining anactive area of the semiconductor substrate; a gate electrode on theactive area; a spacer on a sidewall of the gate electrode, the spacerincluding a lower end closest to the active area among ends of thespacer and an upper end farthest from the active area among ends of thespacer; and impurity regions on opposite sides of the gate electrode,wherein at a height equal to 75% of an overall height of the spacer fromthe lower end, a thickness of the spacer is equal to or greater than 0.4times a thickness of the lower end of the spacer, and the spacerincludes a SiOCN material layer.

A dielectric constant of the SiOCN material layer of the spacer may beless than 5.0.

The SiOCN material layer of the spacer may include about 10 atom % toabout 30 atom % of carbon, and about 25 atom % to about 50 atom % ofoxygen.

The active area may be a fin-type active area that protrudes from thesemiconductor substrate and extends in a first direction, and the gateelectrode may extend on the active area in a direction intersecting withthe first direction.

The gate electrode may intersect the active area and covers two oppositesidewalls of the active area and an upper surface of the active areabetween the two sidewalls.

At a height equal to 50% of the overall height of the spacer from thelower end, a thickness of the spacer may be equal to or greater than 0.8times the thickness of the lower end of the spacer.

The spacer may have an upper surface that is at least partially flat.

The upper surface of the spacer may be at least partially located on thesame plane as an upper surface of the gate electrode.

The embodiments may be realized by providing a method of fabricating asemiconductor device, the method including defining a fin-type activearea that protrudes from a semiconductor substrate and extends in afirst direction; forming a gate electrode that covers two sidewalls andan upper surface of the fin-type active area, the gate electrodeextending in a direction that intersects the first direction; forming aspacer on a sidewall of the gate electrode; and forming impurity regionsin the active area respectively on opposite sides of the gate electrode,wherein forming the spacer includes forming a SiOCN material layer.

Forming the SiOCN material layer may include providing a first carbonprecursor onto the substrate; and providing a second carbon precursoronto the substrate, and the first carbon precursor and the second carbonprecursor may be different materials.

The first carbon precursor may include an alkylsilane having a carbonnumber of 1 to 20, an alkoxysilane having a carbon number of 1 to 20, oran alkylsiloxane having a carbon number of 1 to 20, and the secondcarbon precursor may include an alkylamine having a carbon number of 1to 15 or a nitrogen-containing heterocyclic compound having a carbonnumber of 4 to 15.

The method may further include forming a dummy gate electrode, beforethe forming of the spacer, wherein forming the spacer includes forming aspacer on a sidewall of the dummy gate electrode; and removing the dummygate electrode after the forming of the spacer, wherein forming the gateelectrode is performed after the removing of the dummy gate electrode.

The embodiments may be realized by providing a deposition apparatusincluding a reaction chamber that defines a reaction space; a supportthat supports a substrate; a first transfer line to introduce a firstcarbon precursor into the reaction space; a second transfer line tointroduce a second carbon precursor into the reaction space; andelectrodes to generate a potential to generate plasma within thereaction space, wherein the first carbon precursor and the second carbonprecursor are different materials, and the first transfer line and thesecond transfer line join together in the reaction space.

The support may include a temperature controller to control atemperature of the substrate to 600° C. or less.

The embodiments may be realized by providing a method of forming a SiOCNmaterial layer, the method including providing a substrate; providing anoxygen reactant onto the substrate; providing a first carbon precursoronto the substrate; and providing a second carbon precursor onto thesubstrate, wherein the first carbon precursor and the second carbonprecursor are different materials, and the method is performed at atemperature 600° C. or lower.

The method may further include providing a silicon precursor onto thesubstrate, wherein the silicon precursor is different from the firstcarbon precursor.

The method may further include providing a nitrogen reactant onto thesubstrate, wherein the nitrogen reactant is different from the secondcarbon precursor.

The first carbon precursor may include an alkane having a carbon numberof 1 to 10, an alkene having a carbon number of 2 to 10, an alkylaminehaving a carbon number of 1 to 15, a nitrogen-containing heterocycliccompound having a carbon number of 4 to 15, an alkylsilane having acarbon number of 1 to 20, an alkoxysilane having a carbon number of 1 to20, or an alkylsiloxane having a carbon number of 1 to 20, and thesecond carbon precursor may include an alkane having a carbon number of1 to 10, an alkene having a carbon number of 2 to 10, an alkylaminehaving a carbon number of 1 to 15, a nitrogen-containing heterocycliccompound having a carbon number of 4 to 15, an alkylsilane having acarbon number of 1 to 20, an alkoxysilane having a carbon number of 1 to20, or an alkylsiloxane having a carbon number of 1 to 20.

The first carbon precursor may include an alkylsilane having a carbonnumber of 1 to 20, an alkoxysilane having a carbon number of 1 to 20, oran alkylsiloxane having a carbon number of 1 to 20.

The second carbon precursor may include an alkylamine having a carbonnumber of 1 to 15 or a nitrogen-containing heterocyclic compound havinga carbon number of 4 to 15.

The SiOCN material layer may include about 10 atom % to about 30 atom %of carbon, and about 25 atom % to about 50 atom % of oxygen.

A dielectric constant of the SiOCN material layer may be 1 to 5.

The embodiments may be realized by providing a method of fabricating asemiconductor device, the method including defining a fin-type activearea that protrudes from a semiconductor substrate and extends in afirst direction; forming a gate electrode that covers two sidewalls andan upper surface of the fin-type active area, the gate electrodeextending in a direction that intersects the first direction; forming aspacer on a sidewall of the gate electrode; and forming impurity regionsin the active area respectively on opposite sides of the gate electrode,wherein forming the spacer includes forming a SiOCN material layeraccording to an embodiment.

The embodiments may be realized by providing a material layer stackincluding a semiconductor substrate; and a SiOCN material layer formedover the semiconductor substrate according to an embodiment, wherein theSiOCN material layer includes about 10 atom % to about 30 atom % ofcarbon, and about 25 atom % to about 50 atom % of oxygen.

The embodiments may be realized by providing a semiconductor deviceincluding a semiconductor substrate; an isolation layer defining anactive area of the semiconductor substrate; a gate electrode on theactive area; a spacer on a sidewall of the gate electrode, the spacerincluding a lower end closest to the active area among ends of thespacer and an upper end farthest from the active area among ends of thespacer; and impurity regions on opposite sides of the gate electrode,wherein at a height equal to 75% of an overall height of the spacer fromthe lower end, a thickness of the spacer is equal to or greater than 0.4times a thickness of the lower end of the spacer, and the spacerincludes a SiOCN material layer prepared according to the method of anembodiment.

The embodiments may be realized by providing a deposition apparatus forperforming the method according to an embodiment, the apparatusincluding a reaction chamber that defines a reaction space; a supportthat supports the substrate; a first transfer line to introduce thefirst carbon precursor into the reaction space; a second transfer lineto introduce the second carbon precursor into the reaction space; andelectrodes to generate a potential to generate plasma within thereaction space, wherein the first transfer line and the second transferline join together in the reaction space.

BRIEF DESCRIPTION OF THE DRAWINGS

Features will be apparent to those of skill in the art by describing indetail exemplary embodiments with reference to the attached drawings inwhich:

FIG. 1 illustrates a lateral cross-sectional view of a material layerstack including a semiconductor substrate and a SiOCN material layerformed on the semiconductor substrate, according to an embodiment;

FIG. 2 illustrates a flowchart of a method of fabricating the materiallayer stack, according to an embodiment;

FIG. 3 illustrates a conceptual diagram of plasma enhanced atomic layerdeposition (PEALD) equipment for forming the SiOCN material layer,according to an embodiment;

FIGS. 4A to 4E illustrate timing diagrams of a supply sequence ofprocess gases according to an embodiment;

FIG. 5 illustrates a timing diagram showing a supply sequence of processgases when a second carbon precursor and a nitrogen reactant are thesame;

FIG. 6 illustrates a timing diagram showing a supply sequence of processgases when a silicon precursor and a first carbon precursor are thesame;

FIG. 7 illustrates a timing diagram showing a supply sequence of processgases when a silicon precursor and a first carbon precursor are the sameand a second carbon precursor and a nitrogen reactant are the same;

FIGS. 8A to 8D illustrate a semiconductor device having a SiOCN materiallayer on a semiconductor substrate. For example, FIG. 8A illustrates aplan view of the semiconductor device, FIG. 8B illustrates a perspectiveview of the semiconductor device, FIG. 8C illustrates a lateralcross-sectional view of the semiconductor device, and FIG. 8Dillustrates a magnified cross-sectional view of a gate structure of thesemiconductor device and a structure adjacent to the gate structure;

FIGS. 9A to 9F illustrate cross-sectional views of stages in a method offabricating a semiconductor device, according to an exemplaryembodiment;

FIG. 10 illustrates a block diagram of an electronic device according toan embodiment;

FIG. 11 illustrates a block diagram of a display device including adisplay driving integrated circuit (DDI), according to an embodiment;

FIG. 12 illustrates a circuit diagram of a CMOS inverter according to anembodiment;

FIG. 13 illustrates a circuit diagram of a CMOS SRAM according to anembodiment;

FIG. 14 illustrates a circuit diagram of a CMOS NAND circuit accordingto an embodiment;

FIG. 15 illustrates a block diagram of an electronic system according toan embodiment; and

FIG. 16 illustrates a block diagram of an electronic system according toan embodiment.

DETAILED DESCRIPTION

Example embodiments will now be described more fully hereinafter withreference to the accompanying drawings; however, they may be embodied indifferent forms and should not be construed as limited to theembodiments set forth herein. Rather, these embodiments are provided sothat this disclosure will be thorough and complete, and will fullyconvey exemplary implementations to those skilled in the art.

In the drawing figures, the dimensions of layers and regions may beexaggerated for clarity of illustration. It will also be understood thatwhen a layer or element is referred to as being “on” another layer orelement, it can be directly on the other layer or element, orintervening layers may also be present. In addition, it will also beunderstood that when a layer is referred to as being “between” twolayers, it can be the only layer between the two layers, or one or moreintervening layers may also be present. Like reference numerals refer tolike elements throughout.

As used herein, the term “and/or” includes any and all combinations ofone or more of the associated listed items. For example, the term “or”is not exclusive, and may be understood as having the same meaning as“and/or.” Expressions such as “at least one of,” when preceding a listof elements, modify the entire list of elements and do not modify theindividual elements of the list.

While such terms as “first,” “second,” etc., may be used to describevarious components, such components must not be limited to the aboveterms. The above terms are used only to distinguish one component fromanother. For example, a first component discussed below could be termeda second component, and similarly, a second component may be termed afirst component without departing from the teachings of this disclosure.

The terminology used herein is for the purpose of describing particularembodiments only, and is not intended to be limiting. An expression usedin the singular encompasses the expression in the plural, unless it hasa clearly different meaning in the context. It will be understood thatthe terms, e.g., “comprises,” “includes,” “including,” and/or“comprising,” when used in this specification, specify the presence ofstated features, integers, steps, operations, elements, components,and/or groups thereof, but do not preclude the presence or addition ofone or more other features, integers, steps, operations, elements,components, and/or groups thereof.

Unless otherwise defined, all terms (including technical and scientificterms) used herein have the same meaning as commonly understood by oneof ordinary skill in the art to which this application belongs. It willbe further understood that terms, such as those defined in commonly useddictionaries, should be interpreted as having a meaning that isconsistent with their meaning in the context of the relevant art andwill not be interpreted in an idealized or overly formal sense unlessexpressly so defined herein.

The operations of all methods described herein can be performed in anysuitable order unless otherwise indicated herein or otherwise clearlycontradicted by context. The embodiments are not limited to thedescribed order of the operations. For example, two consecutivelydescribed processes may be performed substantially at the same time orperformed in an order opposite to the described order.

As such, variations from the shapes of the illustrations as a result,for example, of manufacturing techniques and/or tolerances, are to beexpected. Thus, embodiments should not be construed as being limited tothe particular shapes of regions illustrated herein but are to includedeviations in shapes that result, for example, from manufacturing. Theterm “substrate” used in this specification may mean a substrate itself,or a stacked structure including a substrate and a layer or film formedon a surface of the substrate. The term “a surface of a substrate” usedin this specification may mean an exposed surface of a substrate or anouter surface of a layer or film formed on the substrate.

An embodiment may provide a material layer stack including asemiconductor substrate and a SiOCN material layer formed on thesemiconductor substrate.

FIG. 1 illustrates a lateral cross-sectional view of a material layerstack 10 including a semiconductor substrate 11 and a SiOCN materiallayer 12 formed on the semiconductor substrate 11, according to anembodiment.

Referring to FIG. 1, the semiconductor substrate 11 may be formed of,e.g., at least one of a Group III and V element-containing material anda Group IV element-containing material. The Group III and Velement-containing material may be a binary, ternary, or quaternarycompound including at least one Group III element and at least one GroupV element. The Group III and V elements-containing material may be acompound including, as a Group III element, at least one of In, Ga, andAl and, as a Group V element, at least one of As, P, and Sb. Forexample, the Group III and V elements-containing material may beselected from InP, In_(z)Ga_(1-z)As (0≤z≤1), and Al_(z)Ga_(1-z)As(0≤z≤1). The binary compound may include, e.g., one of InP, GaAs, InAs,InSb and GaSb. The ternary compound may be one of InGaP, InGaAs, AlInAs,InGaSb, GaAsSb, and GaAsP. The Group IV element-containing material mayinclude, e.g., Si and/or Ge. In an implementation, the material mayinclude a suitable Group III and V element-containing material and asuitable Group IV element-containing material that are usable to form athin film.

The Group III and V element-containing material, and the Group IVelement-containing material, e.g., Ge, may each be used as a channelmaterial capable of forming a low-power and high-speed transistor. Ahigh-performance CMOS may be formed using a semiconductor substrateformed of a Group III and V element-containing material, e.g., GaAs,having higher mobility of electrons than a Si substrate, and a SiGesemiconductor substrate including a semiconductor material, e.g., Ge,having higher mobility of holes than a Si substrate. According to someembodiments, when an N-type channel is intended to be formed on thesemiconductor substrate 11, the semiconductor substrate 11 may be formedof one of the above-exemplified Group III and V element-containingmaterials or may be formed of SiC. According to some other embodiments,when a P-type channel is intended to be formed on the semiconductorsubstrate 11, the semiconductor substrate 11 may be formed of SiGe.

The SiOCN material layer 12 may be a material layer containing silicon(Si), oxygen (O), carbon (C), and nitrogen (N). In an implementation,the SiOCN material layer 12 may include carbon in an amount of, e.g.,about 10 atom % to about 30 atom %. In an implementation, the SiOCNmaterial layer 12 may include carbon in an amount of, e.g., about 11atom % to about 20 atom %.

In an implementation, the SiOCN material layer 12 may include oxygen inan amount of, e.g., about 25 atom % to about 50 atom %. In animplementation, the SiOCN material layer 12 may include oxygen in anamount of, e.g., about 30 atom % to about 48 atom %.

In an implementation, the SiOCN material layer 12 may include carbon inan amount of, e.g., about 10 atom % to about 30 atom % and oxygen in anamount of, e.g., about 25 atom % to about 50 atom %.

In an implementation, the SiOCN material layer 12 may have a dielectricconstant that is, e.g., greater than or equal to 1 and less than 5.0. Inan implementation, the SiOCN material layer 12 may have a dielectricconstant that is greater than or equal to 1 and less than 4.8. In animplementation, the SiOCN material layer 12 may have a dielectricconstant that is greater than or equal to 1 and less than 4.4. Thedielectric constant may vary depending on the composition of the SiOCNmaterial layer 12.

The SiOCN material layer 12 may be provided directly on thesemiconductor substrate 11 or may be provided on the semiconductorsubstrate 11 with another material layer interposed between the SiOCNmaterial layer 12 and the semiconductor substrate 11. In animplementation, the SiOCN material layer 12 may be stacked on thesemiconductor substrate 11 with an insulation layer interposedtherebetween. In an implementation, the SiOCN material layer 12 may bestacked on the semiconductor substrate 11 with a, e.g., HfO₂, ZrO₂,HfSiO_(x), TaSiO_(x), or LaO_(x) layer interposed therebetween.

In an implementation, a thickness of the SiOCN material layer 12 may notbe constant, as illustrated in FIG. 1. In an implementation, the SiOCNmaterial layer 12 may have a substantially constant thickness.

In an implementation, the SiOCN material layer 12 may be formed on ametal material layer 14. The metal material layer 14 may include, e.g.,titanium (Ti), tungsten (W), aluminum (Al), ruthenium (Ru), niobium(Nb), hafnium (Hf), nickel (Ni), cobalt (Co), platinum (Pt), ytterbium(Yb), terbium (Tb), dysprosium (Dy), erbium (Er), and/or palladium (Pd).

In an implementation, the SiOCN material layer 12 may be formed oncarbide, nitride, silicide, or aluminum carbide of the metals thatconstitute the metal material layer 14, or on a combination thereof.

In an implementation, the SiOCN material layer 12 may be formed directlyon the metal material layer 14 or may be provided on the metal materiallayer 14 with a material layer different from the SiOCN material layer12 interposed therebetween.

In an implementation, the SiOCN material layer 12 may be provided on themetal material layer 14 with a high-k material layer 13 interposedtherebetween. The high-k material layer 13 may be formed of a materialhaving a dielectric constant of, for example, about 10 atom % to about25 atom %. In an implementation, the high-k material layer 13 mayinclude, e.g., hafnium oxide, hafnium oxynitride, hafnium silicon oxide,lanthanum oxide, lanthanum aluminum oxide, lanthanum silicon oxide,zirconium oxide, zirconium silicon oxide, tantalum oxide, tantalumhafnium oxide, tantalum aluminum oxide, tantalum silicon oxide, tantalumzirconium oxide, titanium oxide, titanium aluminum oxide, bariumstrontium titanium oxide, barium titanium oxide, strontium titaniumoxide, yttrium oxide, erbium oxide, dysprosium oxide, gadolinium oxide,gallium oxide, aluminum oxide, aluminum silicon oxide, silicon germaniumoxide, lead scandium tantalum oxide, lead zinc niobate, or a combinationthereof.

In an implementation, the SiOCN material layer 12 may be provided on themetal material layer 14 with a physical property adjustment functionallayer 15 interposed therebetween. In an implementation, the physicalproperty adjustment functional layer 15 may include a barrier metallayer 15 a and a work function adjustment layer 15 b.

The work function adjustment layer 15 b may be an N-type or P-type workfunction adjustment layer. When the work function adjustment layer 15 bis an N-type work function adjustment layer, the work functionadjustment layer 15 b may include, e.g., TiAl, TiAlN, TaC, TiC, and/orHfSi. When the work function adjustment layer 15 b is a P-type workfunction adjustment layer, the work function adjustment layer 15 b mayinclude, e.g., Mo, Pd, Ru, Pt, TiN, WN, TaN, Ir, TaC, RuN, or MoN.

The barrier metal layer 15 a may be, for example, TiN.

A method of fabricating a material layer stack will now be described.

FIG. 2 illustrates a flowchart of a method of fabricating the materiallayer stack, according to an embodiment.

Referring to FIG. 2, a substrate may be carried into a reaction spacesuch as a chamber, in operation S100. To form a SiOCN material layer onthe substrate, precursors may be supplied into the reaction space, inoperation S200. Then, in operation S300, when the SiOCN material layeris formed to have a desired thickness, the substrate may be carried outof the reaction space.

Formation of the SiOCN material layer on the substrate in operation S200may be performed using a suitable method. In an implementation, theSiOCN material layer may be formed by chemical vapor deposition (CVD).In an implementation, the SiOCN material layer may be formed by atomiclayer deposition (ALD). For example, the SiOCN material layer may beformed by plasma enhanced ALD (PEALD).

Formation of the SiOCN material layer on the substrate by PEALD will nowbe described. In an implementation, the SiOCN material layer may beformed using another suitable method.

FIG. 3 illustrates a conceptual diagram of PEALD equipment 900 forforming the SiOCN material layer, according to an embodiment.

Referring to FIG. 3, a pair of conductive flat panel electrodes 932 and934 facing each other and extending in parallel may be provided within areaction space 950, which is the inside of a reaction chamber 940. 13.56MHz or 27 MHz HRF power 962 (and LRF power 964 of no more than 5 MHz(400 kHz to 500 kHz) as needed) may be applied to one of the conductiveflat panel electrodes 932 and 934, and the other electrode may beelectrically grounded as indicated by reference numeral 936. Thus,plasma may be excited between the conductive flat panel electrodes 932and 934.

A lower electrode 932 may serve as a support that supports a substrateW, and a temperature controller 938 may be built into the lowerelectrode 932 to maintain the substrate W at a constant temperature. Forexample, as will be described in detail below, according to embodiments,a SiOCN material layer may be able to be deposited with high oxygen andcarbon contents at a relatively low temperature, e.g., about 600° C. orless. In an implementation, the SiOCN material layer may be depositedwith high oxygen and carbon contents even at about 500° C. or less,which is an even lower temperature, according to the type of carbonprecursor used. In an implementation, the temperature controller 938 maybe configured to control a temperature of the substrate W to 600° C. orless, e.g., 500° C. or less.

An upper electrode 934 may serve as, e.g., a shower head, as well as anelectrode. In an implementation, several gases (including a process gas)may be introduced into the reaction space 950 via the upper electrode934. In an implementation, some gases may be introduced into thereaction space 950 via respective unique pipes of the gases.

A carrier gas 916 may convey different precursors and/or reactants tothe reaction space 950. In an implementation, the carrier gas 916 maypurge an unreacted material or reaction by-products within the reactionspace 950.

In an implementation, the carrier gas 916 may be, e.g., an inert gassuch as helium (He) or neon (Ne), or an extremely-low active gas such asnitrogen (N₂) or carbon dioxide (CO₂).

A silicon precursor 911 may be introduced into the reaction space 950via a silicon precursor supply line 911 s. In an implementation, thesilicon precursor supply line 911 s may be joined to a carrier gassupply line 916 s.

In an implementation, a supply line of the carrier gas 916 may beconnected to supply lines of the silicon precursor 911, an oxygenreactant 914, and a nitrogen reactant 915 as illustrated in FIG. 3. Inan implementation, the supply line of the carrier gas 916 may beconnected to a supply line of a first carbon precursor 912 or a supplyline of a second carbon precursor 913. In an implementation, the firstcarbon precursor 912 may be conveyed by the carrier gas 916 andintroduced into the reaction space 950. In an implementation, the secondcarbon precursor 913 may be conveyed by the carrier gas 916 andintroduced into the reaction space 950.

As shown in FIG. 3, the at least two different first and second carbonprecursors 912 and 913 may be supplied to the reaction space 950 viaspecial supply lines. The first carbon precursor 912 may be supplied tothe reaction space 950 via a first transfer line 912 s. The secondcarbon precursor 913 may be supplied to the reaction space 950 via asecond transfer line 913 s. In an implementation, the first transferline 912 s and the second transfer line 913 s may not be joined togetherbefore they reach the reaction space 950.

The first carbon precursor 912 and the second carbon precursor 913 mayeach independently include, e.g., an alkane having a carbon number of 1to 10, an alkene having a carbon number of 2 to 10, an alkylamine havinga carbon number of 1 to 15, a nitrogen-containing heterocyclic compoundhaving a carbon number of 4 to 15, an alkylsilane having a carbon numberof 1 to 20, an alkoxysilane having a carbon number of 1 to 20, and/or analkylsiloxane having a carbon number of 1 to 20.

The alkane having a carbon number of 1 to 10 may include, e.g., methane,ethane, propane, butane (all isomers), pentane (all isomers), hexane(all isomers), heptane (all isomers), octane (all isomers), nonane (allisomers), decane (all isomers), or a mixture thereof.

The alkene having a carbon number of 2 to 10 may include, e.g.,ethylene, propylene, butene (all isomers), hexene (all isomers), heptene(all isomers), octene (all isomers), nonene (all isomers), decene (allisomers), or a mixture thereof.

The alkylamine having a carbon number of 1 to 15 may have, e.g., theformula NR¹R²R³. In an implementation, R¹, R², and R³ may eachindependently be, e.g., hydrogen, an halogen element, an alkyl having acarbon number of 1 to 10, an alkenyl having a carbon number of 1 to 10,an alkylamine having a carbon number of 1 to 10, an aryl having a carbonnumber of 6 to 12, an aryl alkyl having a carbon number of 7 to 12, analkyl aryl having a carbon number of 7 to 12, and/or a cycloalkyl havinga carbon number of 5 to 12. In an implementation, at least one of R¹,R², and R³ may be, e.g., an alkyl having a carbon number of 1 to 10. Inan implementation, two of R¹, R², and R³ may be connected to each otherto form a ring. In an implementation, two or more alkylamines may beconnected to each other to form alkyldiamine, alkyltriamine, or thelike, and alkyldiamine, alkyltriamine, or the like may belong to thealkylamine having a carbon number of 1 to 15.

Examples of the alkylamine having a carbon number of 1 to 15 may includemonomethylamine, dimethyl amine, trimethyl amine, monoethylamine,diethylamine, triethylamine, mono-propyl amine (all isomers),dipropylamine (all isomers), tripropylamine (all isomers), mono-butylamine (all isomers), dibutylamine (all isomers), tributylamine (allisomers), mono-pentyl amine (all isomers), dipentylamine (all isomers),tripentylamine (all isomers), mono-hexyl amine (all isomers),dihexylamine (all isomers), mono-heptyl amine (all isomers),diheptylamine (all isomers), mono-octyl amine (all isomers), mono-nonylamine (all isomers), mono-decyl amine (all isomers), mono-undecyl amine(all isomers), mono-dodecyl amine (all isomers), mono-tridecyl amine(all isomers), mono-tetradecyl amine (all isomers), mono-pentadecylamine (all isomers), dimethyl (ethyl) amine (all isomers), dimethyl(propyl) amine (all isomers), dimethyl (butyl) amine (all isomers),dimethyl (pentyl) amine (all isomers), dimethyl (hexyl) amine (allisomers), dimethyl (heptyl) amine (all isomers), dimethyl (octyl) amine(all isomers), dimethyl (nonyl) amine (all isomers), dimethyl (decyl)amine (all isomers), dimethyl (undecyl) amine (all isomers), dimethyl(dodecyl) amine (all isomers), dimethyl (tridecyl) amine (all isomers),diethyl (methyl) amine (all isomers), diethyl (propyl) amine (allisomers), diethyl (butyl) amine (all isomers), diethyl (pentyl) amine(all isomers), diethyl (hexyl) amine (all isomers), diethyl (heptyl)amine (all isomers), diethyl (octyl) amine (all isomers), diethyl(nonyl) amine (all isomers), diethyl (decyl) amine (all isomers),diethyl (undecyl) amine (all isomers), dipropyl (methyl) amine (allisomers), dipropyl (ethyl) amine (all isomers), dipropyl (butyl) amine(all isomers), dipropyl (pentyl) amine (all isomers), dipropyl (hexyl)amine (all isomers), dipropyl (heptyl) amine (all isomers), dipropyl(octyl) amine (all isomers), dipropyl (nonyl) amine (all isomers),dibutyl (methyl) amine (all isomers), dibutyl (ethyl) amine (allisomers), dibutyl (propyl) amine (all isomers), dibutyl (pentyl) amine(all isomers), dibutyl (hexyl) amine (all isomers), dibutyl (heptyl)amine (all isomers), dipentyl (methyl) amine (all isomers), dipentyl(ethyl) amine (all isomers), dipentyl (propyl) amine (all isomers),dipentyl (butyl) amine (all isomers), dihexyl (methyl) amine (allisomers), dihexyl (ethyl) amine (all isomers), dihexyl (propyl) amine(all isomers), diheptyl (methyl) amine (all isomers), dimethyl (butenyl)amine (all isomers), dimethyl (pentenyl) amine (all isomers), dimethyl(hexenyl) amine (all isomers), dimethyl (heptenyl) amine (all isomers),dimethyl (octenyl) amine (all isomers), dimethyl (cyclopentenyl) amine(all isomers), dimethyl (cyclohexyl) amine (all isomers), dimethyl(cycloheptyl) amine (all isomers), bis (methyl cyclopentyl) amine (allisomers), (dimethyl cyclopentyl) amine (all isomers), bis (dimethylcyclopentyl) amine (all isomers), (ethyl cyclopentyl) amine (allisomers), bis (ethylcyclopentyl) amine (all isomers), (methylethylcyclopentyl) amine (all isomers), bis (methylethyl cyclopentyl) amine(all isomers), N-methyl ethylene diamine (all isomers), N-ethyl ethylenediamine (all isomers), N-propyl ethylene diamine (all isomers), N-butylethylene diamine (all isomers), N-pentyl ethylene diamine (all isomers),N-hexyl ethylene diamine (all isomers), N-heptyl ethylene diamine (allisomers), N-octyl ethylene diamine (all isomers), N-nonyl ethylenediamine (all isomers), N-decyl 1 ethylene diamine (all isomers),N-undecyl ethylene diamine (all isomers), and N-dodecyl ethylene diamine(all isomers).

The nitrogen-containing heterocyclic compound having a carbon number of4 to 15 may include, e.g., at least one compound of the followingFormula 1 to Formula 8:

In Formulae 1 to 8, n may be an integer of 1 to 4 and R may be, e.g.,hydrogen, an alkyl having a carbon number of 1 to 10, an alkenyl havinga carbon number of 1 to 10, an aryl having a carbon number of 6 to 12,an aryl alkyl having a carbon number of 7 to 12, an alkyl aryl having acarbon number of 7 to 12, and/or a cycloalkyl having a carbon number of5 to 12.

The alkylsilane having a carbon number of 1 to 20 may have, e.g., theformula R¹—(SiR²R³)n-R⁴. In an implementation, n may be an integer of 1to 12 and R¹, R², R³, and R⁴ may each independently be, e.g., hydrogen,an halogen element, an alkyl having a carbon number of 1 to 10, analkenyl having a carbon number of 1 to 10, an alkylamino having a carbonnumber of 1 to 10, an aryl having a carbon number of 6 to 12, an arylalkyl having a carbon number of 7 to 12, an alkyl aryl having a carbonnumber of 7 to 12, and/or a cycloalkyl having a carbon number of 5 to12. In an implementation, at least one of R¹, R², R³, and R⁴ may includecarbon atoms that are directly combined with Si. In an implementation,R¹ and R⁴ may be connected to each other to form a ring.

Examples of the alkylsilane having a carbon number of 1 to 20 mayinclude methylsilane, tetramethylsilane (TMS), tetraethylsilane (TES),tetrapropylsilane, tetrabutylsilane, dimethylsilane (DMS), diethylsilane(DES), dimethyldifluorosilane (DMDFS), dimethyldichlorosilane (DMDCS),diethyldichlorosilane (DEDCS), hexamethyldisilane,dodecamethylcyclohexasilane, dimethyldiphenylsilane,diethyldiphenylsilane, methyltrichlorosilane, methyltriphenylsilane, anddimethyldiethylsilane.

The alkoxysilane having a carbon number of 1 to 20 may be a compound inwhich substituted or unsubstituted alkoxy groups are combined with asilicon atom at the center, and may have, e.g., the formulaR¹—(SiR²R³)n-R⁴. In an implementation, n may be an integer of 1 to 12and R¹, R², R³, and R⁴ may each independently be, e.g., hydrogen, anhalogen element, an alkyl having a carbon number of 1 to 10, an alkoxyhaving a carbon number of 1 to 10, an alkenyl having a carbon number of1 to 10, an alkylamino having a carbon number of 1 to 10, an aryl havinga carbon number of 6 to 12, an aryl alkyl having a carbon number of 7 to12, an alkyl aryl having a carbon number of 7 to 12, and/or a cycloalkylhaving a carbon number of 5 to 12. In an implementation, at least one ofR¹, R², R³, and R⁴ may be an alkoxy having a carbon number of 1 to 10,and/or at least one of R¹, R², R³, and R⁴ may include carbon atoms thatare directly combined with Si. In an implementation, R¹ and R⁴ may beconnected to each other to form a ring.

Examples of the alkoxysilane having a carbon number of 1 to 20 mayinclude trimethoxysilane (TMOS), dimethoxysilane (DMOS), methoxysilane(MOS), methyldimethoxysilane (MDMOS), diethoxymethylsilane (DMES),dimethylethoxysilane, dimethylaminomethoxysilane (DMAMES),dimethylmethoxysilane (DMMOS), methyltrimethoxysilane,dimethyldimethoxysilane, phenyltrimethoxysilane,diphenyldimethoxysilane, diphenyldiethoxysilane, triphenylmethoxysilane,and triphenylethoxysilane.

The alkylsiloxane having a carbon number of 1 to 20 may include two ormore silicon atoms connected to each other with oxygen atoms interposedtherebetween, and may have, e.g., the formula R¹—([SiR²R³]—O)n-R⁴. In animplementation, n may be an integer of 2 to 12 and R¹, R², R³, and R⁴may each independently be, e.g., hydrogen, a halogen element, an alkylhaving a carbon number of 1 to 10, an alkoxy having a carbon number of 1to 10, an alkenyl having a carbon number of 1 to 10, an alkylaminohaving a carbon number of 1 to 10, an aryl having a carbon number of 6to 12, an aryl alkyl having a carbon number of 7 to 12, an alkyl arylhaving a carbon number of 7 to 12, and/or a cycloalkyl having a carbonnumber of 5 to 12. In an implementation, at least one of R¹, R², R³, andR⁴ may include carbon atoms that are directly combined with Si. In animplementation, R¹ and R⁴ may be connected to each other to form a ring.

Examples of the alkylsiloxane having a carbon number of 1 to 20 mayinclude hexamethylcyclotrisiloxane, tetramethylcyclotetrasiloxane,tetraethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, andhexamethyldisiloxane.

In an implementation, at least one of the alkylsilane having a carbonnumber of 1 to 20, alkoxysilane having a carbon number of 1 to 20, andalkylsiloxane having a carbon number of 1 to 20 described above may havea molecular weight of about 50 to about 1,000. In an implementation, atleast one of the alkylsilane having a carbon number of 1 to 20,alkoxysilane having a carbon number of 1 to 20, and alkylsiloxane havinga carbon number of 1 to 20 may have a molecular weight of about 100 toabout 400.

In an implementation, the silicon precursor may include, e.g., silane(SiH₄), disilane (Si₂H₆), monochlorosilane (SiClH₃), dichlorosilane(SiCl₂H₂), trichlorosilane (SiCl₃H), hexachlorodisilane (Si₂Cl₆),diethyl silane (Et₂SiH₂), tetraethyl orthosilicate (Si(OCH₂CH₃)₄, TEOS),or alkyl amino silane-based compounds. The alkyl amino silane-basedcompound may include, e.g., diisopropylan amino silane(H₃Si(N(i-Prop)₂)), bis (tertiary-butylan amino) silane((C₄H₉(H)N)₂SiH₂), tetrakise (dimethylan amino) silane (Si(NMe₂)₄),tetrakise (ethylmethylan amino) silane (Si(NEtMe)₄), tetrakise(diethylan amino) silane (Si(NEt₂)₄), tris (dimethylan amino) silane(HSi(NMe₂)₃), tris (ethylmethylan amino) silane (HSi(NEtMe)₃), tris(diethylan amino) silane (HSi(NEt₂)₃), tris (dimethyl hydrazino) silane(HSi(N(H)NMe₂)₃), bis (diethylan amino) silane (H₂Si(NEt₂)₂),bis(diisopropylan amino) silane (H₂Si(N(i-Prop)₂)₂), tris (isopropylanamino) silane (HSi(N(i-Prop)₂)₃), or (diisopropylan amino) silane(H₃Si(N(i-Prop)₂).

Herein, Me represents a methyl group, Et represents an ethyl group,i-Prop represents an iso-propyl group, n-Prop represents an n-propylgroup, Bu represents a butyl group, n-Bu represents an n-butyl group, Cprepresents a cyclopentadienyl group, THD represents2,2,6,6-tetramethyl-3,5-heptanedionate, TMPD represents2,2,6,6-tetramethyl-p-phenylenediamine, acac represents acetylacetonate,hfac represents hexafluoro acetylacetonate, and FOD represents6,6,7,7,8,8,8-heptfluoro-2,2-dimethyl-3,5-octane dionate.

In an implementation, the oxygen reactant may include, e.g., O₃, H₂O,O₂, NO₂, NO, N₂O, H₂O, alcohol, metal alkoxide, plasma O₂, remote plasmaO₂, plasma N₂O, plasma H₂O, or a combination thereof. In animplementation, the nitrogen reactant may include, e.g., N₂, NH₃,hydrazine (N₂H₄), plasma N₂, remote plasma N₂, or a combination thereof.

A sequence in which the above-described process gases are supplied intothe reaction space 950 will now be described.

FIG. 4A illustrates a timing diagram of a supply sequence of processgases according to an embodiment.

Referring to FIG. 4A, process gases may be sequentially supplied intothe reaction space 950 in the order of, e.g., a silicon precursor, anoxygen reactant, a first carbon precursor, a second carbon precursor,and a nitrogen precursor. Supply timings of these process gases may beseparated from one another by supply timings of a purge gas.

In an implementation, the process gases may be sequentially suppliedinto the reaction space 950 in the order of a silicon precursor, anoxygen reactant, a first carbon precursor, a second carbon precursor,and a nitrogen precursor as illustrated in FIG. 4A. In animplementation, the supply order may appropriately vary depending on,e.g., reaction activity between a precursor and each reactant.

In an implementation, pulse supplies of the silicon precursor, theoxygen reactant, the first carbon precursor, the second carbonprecursor, and the nitrogen precursor may form a single cycle. The cyclemay repeat until the SiOCN material layer is formed to have a desiredthickness.

In an implementation, at least one of the first carbon precursor and thesecond carbon precursor may be, e.g., (i) alkylamine having a carbonnumber of 1 to 15 and/or a nitrogen-containing heterocyclic compoundhaving a carbon number of 4 to 15; or (ii) alkylsilane having a carbonnumber of 1 to 20, alkoxysilane having a carbon number of 1 to 20,and/or alkylsiloxane having a carbon number of 1 to 20.

In an implementation, the first carbon precursor may be alkylaminehaving a carbon number of 1 to 15 and/or a nitrogen-containingheterocyclic compound having a carbon number of 4 to 15, and the secondcarbon precursor may be one of the previously-described compounds, e.g.,an alkane having a carbon number of 1 to 10 and/or alkene having acarbon number of 2 to 10.

In an implementation, the first carbon precursor may be alkylsilanehaving a carbon number of 1 to 20, alkoxysilane having a carbon numberof 1 to 20, and/or alkylsiloxane having a carbon number of 1 to 20, andthe second carbon precursor may be one of the previously-describedcompounds, e.g., an alkane having a carbon number of 1 to 10 and/oralkene having a carbon number of 2 to 10.

In an implementation, the first carbon precursor may be one of thepreviously-described compounds, e.g., an alkane having a carbon numberof 1 to 10 and/or alkene having a carbon number of 2 to 10, and thesecond carbon precursor may be alkylamine having a carbon number of 1 to15 and/or a nitrogen-containing heterocyclic compound having a carbonnumber of 4 to 15.

In an implementation, the first carbon precursor may be one of thepreviously-described compounds, e.g., alkane having a carbon number of 1to 10 and/or alkene having a carbon number of 2 to 10, and the secondcarbon precursor may be alkylsilane having a carbon number of 1 to 20,alkoxysilane having a carbon number of 1 to 20, and/or alkylsiloxanehaving a carbon number of 1 to 20.

When the first carbon precursor and the second carbon precursor arecomposed as described above, a high oxygen content and a high carboncontent may be secured even at a relatively low process temperature,e.g., of 600° C. or less. The high carbon content may result in animprovement of tolerance to etching. The high oxygen content may resultin a reduction in a dielectric constant. For example, the dielectricconstant may be reduced to be less than 5.0 via material selection asdescribed above.

FIG. 4B illustrates a timing diagram of a supply sequence of processgases according to another embodiment.

The embodiment of FIG. 4B is different from that of FIG. 4A in that thefirst carbon precursor may be supplied after the second carbon precursoris supplied. The first carbon precursor and the second carbon precursormay be different in terms of affinity with a surface, chemisorptioncharacteristics, and reactivity with another reactant, and theproperties of a subsequently obtained material layer may vary with anchange in the supply sequence.

FIGS. 4C to 4E illustrate timing diagrams showing a supply sequence ofprocess gases according to other embodiments.

The embodiment of FIG. 4C is different from those of FIGS. 4A and 4B inthat the first carbon precursor and the second carbon precursor may besupplied at the same time. For example, when the first carbon precursorand the second carbon precursor have similar chemisorptioncharacteristics, this supply method may be used.

The embodiment of FIG. 4D is different from those of FIGS. 4A to 4C inthat, the supply times of the first carbon precursor and the secondcarbon precursor overlap with each other, but supplying the first carbonprecursor starts before the second carbon precursor is supplied and endsafter the supply of the second carbon precursor is stopped. For example,when the second carbon precursor is supplied to adjust the content of aspecific component of a subsequently obtained material layer, thissupplying method may be used.

In an implementation, a supplying method performed in reverse comparedto the above-described supplying method may be used in consideration ofaffinity with a surface, chemisorption characteristics, and reactivitywith another reactant of each of the first carbon precursor and thesecond carbon precursor. For example, supply of the second carbonprecursor may start before the first carbon precursor is supplied andend after the supply of the first carbon precursor is stopped.

Referring to FIG. 4E, supply of the first carbon precursor maytemporally and/or partially overlap with supply of the second carbonprecursor. As shown in FIG. 4E, supply of the first carbon precursor maystart before supply of the second carbon precursor starts, supply of thesecond carbon precursor may start before supply of the first carbonprecursor ends, and supply of the second carbon precursor may end aftersupply of the first carbon precursor ends. This supplying method may beused to correct, e.g., a difference between respective chemisorptioncharacteristics of the first carbon precursor and the second carbonprecursor.

In an implementation, a supplying method reverse to the above-describedsupplying method may be used in consideration of affinity with asurface, chemisorption characteristics, and reactivity with anotherreactant of each of the first carbon precursor and the second carbonprecursor. For example, supply of the second carbon precursor may startbefore supply of the first carbon precursor starts, supply of the firstcarbon precursor may start before supply of the second carbon precursorends, and supply of the first carbon precursor may end after supply ofthe second carbon precursor ends.

In an implementation, when alkylamine having a carbon number of 1 to 15or a nitrogen-containing heterocyclic compound having a carbon number of4 to 15 is used as the second carbon precursor, nitrogen atoms may beincluded in the second carbon precursor, and supply of a nitrogenreactant may be omitted. For example, the second carbon precursor andthe nitrogen reactant may be the same materials, and thus may besupplied in an identical or in a single operation.

FIG. 5 illustrates a timing diagram showing a supply sequence of processgases when the second carbon precursor and the nitrogen reactant are onein the same.

Referring to FIG. 5, the process gases may be sequentially supplied intothe reaction space 950 in the order of a silicon precursor, an oxygenreactant, a first carbon precursor, and a second carbon precursor (i.e.,the same as a nitrogen reactant). Supply pulses of these process gasesmay be separated from one another by supply pulses of a purge gas.

In an implementation, the process gases may be sequentially suppliedinto the reaction space 950 in the order of a silicon precursor, anoxygen reactant, a first carbon precursor, and a second carbon precursor(i.e., a nitrogen reactant) as illustrated in FIG. 5. In animplementation, the supply order may appropriately vary depending on,e.g., reaction activity between a precursor and each reactant.

In an implementation, pulse supplies of the silicon precursor, theoxygen reactant, the first carbon precursor, and the second carbonprecursor (i.e., a nitrogen reactant) may form a single cycle. The cyclemay be repeated until the SiOCN material layer is formed to have adesired thickness.

In the embodiment of FIG. 5, the first carbon precursor and the secondcarbon precursor may be sequentially supplied, and supply pulses of thefirst and second carbon precursors may be separated from each other bythe supply pulses of the purge gas. In an implementation, according tothe characteristics of precursors and reactants, methods of supplyingthe first carbon precursor and the second carbon precursor as describedabove with reference FIGS. 4B-4E may be employed in the embodiment ofFIG. 5.

In an implementation, when at least one of alkylsilane having a carbonnumber of 1 to 20, alkoxysilane having a carbon number of 1 to 20, andalkylsiloxane having a carbon number of 1 to 20 is used as the firstcarbon precursor, silicon atoms may be included in the first carbonprecursor, and supply of a silicon precursor may be omitted. Forexample, the silicon precursor and the first carbon precursor may be thesame materials and thus may be supplied in an identical or a singleoperation.

FIG. 6 illustrates a timing diagram showing a supply sequence of processgases when the silicon precursor and the first carbon precursor are onein the same.

Referring to FIG. 6, process gases may be sequentially supplied into thereaction space 950 in the order of a silicon precursor (i.e., the sameas a first carbon precursor), an oxygen reactant, a second carbonprecursor, and a nitrogen reactant. Supply pulses of these process gasesmay be separated from one another by supply pulses of a purge gas.

In an implementation, the process gases may be sequentially suppliedinto the reaction space 950 in the order of a silicon precursor (i.e., afirst carbon precursor), an oxygen reactant, a second carbon precursor,and a nitrogen reactant as illustrated in FIG. 6. In an implementation,the supply order may appropriately vary depending on, e.g., reactionactivity between a precursor and each reactant.

In an implementation, pulse supplies of the silicon precursor (i.e., afirst carbon precursor), the oxygen reactant, the second carbonprecursor, and the nitrogen reactant may form a single cycle. The cyclemay be repeated until the SiOCN material layer is formed to have adesired thickness.

In the embodiment of FIG. 6, the silicon precursor (i.e., the firstcarbon precursor) and the second carbon precursor may be sequentiallysupplied, and supply pulses of the silicon precursor and the secondcarbon precursor may be separated from each other by the supply pulsesof the purge gas. In an implementation, according to the characteristicsof precursors and reactants, methods of supplying the silicon precursor(i.e., the first carbon precursor) and the second carbon precursor asdescribed above with reference FIGS. 4B-4E may be employed in theembodiment of FIG. 6.

In an implementation, at least one of an alkylsilane having a carbonnumber of 1 to 20, an alkoxysilane having a carbon number of 1 to 20, oran alkylsiloxane having a carbon number of 1 to 20 may be used as thefirst carbon precursor, and an alkylamine having a carbon number of 1 to15 or a nitrogen-containing heterocyclic compound having a carbon numberof 4 to 15 may be used as the second carbon precursor. In this case,supply of the silicon precursor may be omitted because silicon atoms maybe included in and provided from the first carbon precursor, and supplyof the nitrogen reactant may be omitted because nitrogen atoms may beincluded in and provided from the second carbon precursor. For example,the silicon precursor and the first carbon precursor may be the samematerials and thus may be supplied in an identical or a singleoperation. The second carbon precursor and the nitrogen reactant may bethe same materials and thus may be supplied in an identical or singleoperation.

FIG. 7 illustrates a timing diagram showing a supply sequence of processgases when the silicon precursor and the first carbon precursor are onein the same and the second carbon precursor and the nitrogen reactantare one in the same.

Referring to FIG. 7, process gases may be sequentially supplied into thereaction space 950 in the order of a silicon precursor (i.e., also afirst carbon precursor), an oxygen reactant, and a second carbonprecursor (i.e., also a nitrogen reactant). Supply pulses of theseprocess gases may be separated from one another by supply pulses of apurge gas.

In an implementation, the process gases may be sequentially suppliedinto the reaction space 950 in the order of a silicon precursor (i.e., afirst carbon precursor), an oxygen reactant, and a second carbonprecursor (i.e., a nitrogen reactant) as illustrated in FIG. 7. In animplementation, the supply order may appropriately vary depending on,e.g., reaction activity between a precursor and each reactant.

In an implementation, pulse supplies of the silicon precursor (i.e., thefirst carbon precursor), the oxygen reactant, and the second carbonprecursor (i.e., the nitrogen reactant) may form a single cycle. Thecycle may be repeated until the SiOCN material layer is formed to have adesired thickness.

In the embodiment of FIG. 7, the silicon precursor (also the firstcarbon precursor) and the second carbon precursor (also the nitrogenreactant) may be sequentially supplied, and supply pulses of the siliconprecursor and the second carbon precursor may be separated from eachother by the supply pulses of the purge gas. In an implementation,according to the characteristics of precursors and reactants, methods ofsupplying the silicon precursor (i.e., the first carbon precursor) andthe second carbon precursor (i.e., the nitrogen reactant) as describedabove with reference FIGS. 4B-4E may be employed in the embodiment ofFIG. 7.

By using at least one of alkylsilane having a carbon number of 1 to 20,alkoxysilane having a carbon number of 1 to 20, or alkylsiloxane havinga carbon number of 1 to 20 as the first carbon precursor, and usingalkylamine having a carbon number of 1 to 15 or a nitrogen-containingheterocyclic compound having a carbon number of 4 to 15 as the secondcarbon precursor, a high oxygen content and a high carbon content may besecured even at a significantly low temperature of, e.g., 500° C. orless. The high carbon content may result in an improvement of toleranceto etching. The high oxygen content may result in a reduction in adielectric constant. For example, a dielectric constant of a layerformed may be reduced to be less than 4.4 via material selection asdescribed above.

A semiconductor device including the material layer stack will now bedescribed.

FIGS. 8A to 8D illustrate a semiconductor device 100 having a SiOCNmaterial layer on a semiconductor substrate. FIG. 8A illustrates a planview of the semiconductor device 100, FIG. 8B illustrates a perspectiveview of the semiconductor device 100, FIG. 8C illustrates a lateralcross-sectional view of the semiconductor device 100, and FIG. 8Dillustrates a magnified cross-sectional view of a gate structure 120 ofthe semiconductor device 100 and a structure adjacent to the gatestructure 120.

Referring to FIGS. 8A to 8D, the semiconductor device 100 may include afin-type active area FA protruding from a substrate 102.

The substrate 102 may include a semiconductor such as Si or Ge, or acompound semiconductor such as SiGe, SiC, GaAs, InAs, or InP. In animplementation, the substrate 102 may be formed of at least one of aGroup III and V element-containing material and a Group IVelement-containing material. The Group III and V element-containingmaterial may be a binary, ternary, or quaternary compound including atleast one Group III element and at least one Group V element. The GroupIII and V element-containing material may be a compound including, as aGroup III element, at least one of In, Ga, and Al and, as a Group Velement, at least one of As, P, and Sb. For example, the Group III and Velements-containing material may be selected from InP, In_(z)Ga_(1-z)As(0≤z≤1), and Al_(z)Ga_(1-z)As (0≤z≤1). The binary compound may be one ofInP, GaAs, InAs, InSb and GaSb, for example. The ternary compound may beone of InGaP, InGaAs, AlInAs, InGaSb, GaAsSb, and GaAsP. The Group IVelement-containing material may be Si or Ge. In an implementation, asuitable Group III and V element-containing material and a suitableGroup IV element-containing material that are usable by an IC device maybe used. In an implementation, the substrate 102 may have asilicon-on-insulator (SOI) structure. The substrate 102 may include aconductive region, for example, an impurity-doped well or animpurity-doped structure.

The substrate 102 may be formed of the Group III and Velement-containing material or the Group IV element-containing material,and the substrate 102 may be used as a channel material capable offorming a low-power and high-speed transistor. When an NMOS transistoris formed on the substrate 102, the substrate 102 may be formed of oneof the above-exemplified Group III and V elements-containing materials.For example, the substrate 102 may be formed of GaAs. When a PMOStransistor is formed on the substrate 102, the substrate 102 may beformed of a semiconductor material having a higher mobility of holes,for example, Ge, compared with a Si substrate.

The fin-type active area FA may extend in one direction (Y direction inFIGS. 8A and 8B). An isolation layer 110 covering a lower sidewall ofthe fin-type active area FA is formed on the substrate 102. The fin-typeactive area FA protrudes in a fin shape on the isolation layer 110. Inan implementation, the isolation layer 110 may be formed of a siliconoxide layer, a silicon nitride layer, a silicon oxynitride layer, or acombination thereof.

On the fin-type active area FA on the substrate 110, the gate structure120 may extend in a direction (X direction) that intersects an extendingdirection of the fin-type active area FA. A pair of source/drain regions130 may be formed on portions of the fin-type active area FA that are onboth, e.g., opposite, sides of the gate structure 120.

The source/drain areas 130 may include a semiconductor layer epitaxiallygrown from the fin-type active area FA. Each of the source/drain regions130 may be formed of an embedded SiGe structure including a plurality ofepitaxially grown SiGe layers, an epitaxially grown Si layer, or anepitaxially grown SiC layer. In an implementation, the source/drainareas 130 may have a specific shape as illustrated in FIG. 8B. In animplementation, the source/drain areas 130 may have various shapes. Forexample, the source/drain areas 130 may have any of variouscross-sectional shapes such as a circle, an oval, and a polygon.

A MOS transistor TR may be formed at an intersection between thefin-type active area FA and the gate structure 120. The MOS transistorTR is a three-dimensional (3D) MOS transistor in which a channel isformed on an upper surface and both lateral surfaces of the fin-typeactive area FA. The MOS transistor TR may constitute an NMOS transistoror a PMOS transistor.

As shown in FIG. 8C, the gate structure 120 may include an interfacelayer 112, a high-dielectric constant layer 114, a firstmetal-containing layer 126A, a second metal-containing layer 126B, and agap-fill metal layer 128 sequentially formed on a surface of thefin-type active area FA. The first metal-containing layer 126A, thesecond metal-containing layer 126B, and the gap-fill metal layer 128 ofthe gate structure 120 may constitute a gate electrode 120G.

Insulation spacers 142 may be formed on sidewalls, e.g., both sidewalls,of the gate structure 120. The insulation spacers 142 may be or mayinclude, e.g., SiOCN material layers. In an implementation, each of theinsulation spacers 142 may be formed as a single layer. In animplementation, each of the insulation spacers 142 may be formed as amulti-layer in which at least two material layers are stacked.

In an implementation, the SiOCN material layer of the insulation spacer142 may have a dielectric constant that is greater than or equal to 1and less than 5.0. In an implementation, the SiOCN material layer of theinsulation spacer 142 may have a dielectric constant that is greaterthan 1 or equal to and less than 4.8. In an implementation, the SiOCNmaterial layer of the insulation spacer 142 may have a dielectricconstant that is greater than or equal to 1 and less than 4.4.

When the SiOCN material layer includes carbon in an amount of, e.g.,about 10 atom % to about 30 atom % and oxygen in an amount of, e.g.,about 25 atom % to about 50 atom %, a desirably low dielectric constantmay be achieved. In an implementation, the carbon content may be about11 atom % to about 20 atom %. In an implementation, the oxygen contentmay be about 30 atom % to about 48 atom %. In an implementation, thecarbon content may be about 15 atom % to about 20 atom %. In animplementation, the oxygen content may be about 38 atom % to about 48atom %.

As shown in FIG. 8D, the insulation spacer 142 may have a height H1 andmay include an upper end 142 t and a lower end 142 b. The upper end 142t may be a portion of the insulation spacer 142 that is farthest from(e.g., distal to) the fin-type active area FA. The lower end 142 b maybe a portion of the insulation spacer 142 that is closest to (e.g.,adjacent to or contacting) the fin-type active area FA.

The insulation spacer 142 may have such a shape that a thickness thereof(e.g., in a lateral direction) decreases along a direction from thelower end 142 b to the upper end 142 t. For example, a thickness of theinsulation spacer 142 may be reduced as a height thereof, e.g., adistance from the fin-type active area FA, increases. In animplementation, the lower end 142 b of the insulation spacer 142 mayhave a plane that is at least partially flat. In an implementation, thelower end 142 b of the insulation spacer 142 may be located on the sameplane as a lower surface of the interface layer 112.

In an implementation, the upper end 142 t of the insulation spacer 142may have a plane or part that is at least partially flat. In animplementation, the upper end 142 t of the insulation spacer 142 may belocated on the same plane as an upper surface of the gate electrode120G.

When the insulation spacer 142 includes a SiOCN material layer asdescribed above, the insulation spacer 142 may have a relatively strongetching resistance, and a thickness of an upper portion of theinsulation spacer 142 (e.g., in the lateral direction) may be greaterthan that of a spacer formed of other types of material layers. Forexample, less of the insulation spacer 142 may be removed during anetching process for forming a device, and as a result, thicknesses ofthe insulation spacer 142 may be greater. As shown in FIG. 8D, when theinsulation spacer 142 has the height H1 as an overall height, the lowerend 142 b may have a thickness t1. At a height H2 (corresponding to 75%of the overall height of the insulation spacer 142 from the lower end142 b), the insulation spacer 142 may have a thickness t2 that may beequal to or greater than 0.4 times the thickness t1 (e.g., and less thanor equal to the thickness t1). At a height H3 corresponding to 50% ofthe overall height of the insulation spacer 142 from the lower end 142b, the insulation spacer 142 may have a thickness t3 that may be equalto or greater than 0.8 times the thickness t1 (e.g., and less than orequal to the thickness t1).

In an implementation, at the height H2 corresponding to 75% of theoverall height of the insulation spacer 142 from the lower end 142 b,the insulation spacer 142 may have a thickness t2 that may be equal toor greater than 0.5 times the thickness t1 (e.g., and less than or equalto the thickness t1). At the height H3 corresponding to 50% of theoverall height of the insulation spacer 142 from the lower end 142 b,the insulation spacer 142 may have a thickness t3 that may be equal toor greater than 0.9 times the thickness t1 (e.g., and less than or equalto the thickness t1).

In an implementation, an interlayer insulation layer 144 may be formedon the insulation spacers 142.

The interface layer 112 may be formed on a surface of the fin-typeactive area FA. The interface layer 112 may be formed of an insulationmaterial, such as, an oxide layer, a nitride layer, or an oxynitridelayer. The interface layer 112 may constitute a gate insulation layer,together with the high-dielectric constant layer 114.

The high dielectric layer 114 may be formed of a material having ahigher dielectric constant than a silicon oxide layer. For example, thehigh-dielectric constant layer 114 may have a dielectric constant ofabout 10 to about 25. The high dielectric layer 114 may be formed ofzirconium oxide, zirconium silicon oxide, hafnium oxide, hafniumoxynitride, hafnium silicon oxide, tantalum oxide, titanium oxide,barium strontium titanium oxide, barium titanium oxide, strontiumtitanium oxide, yttrium oxide, aluminum oxide, lead scandium tantalumoxide, lead zinc niobate, or a combination thereof.

In an implementation, the first metal-containing layer 126A may includenitride of Ti, nitride of Ta, oxynitride of Ti, or oxynitride of Ta. Forexample, the first metal-containing layer 126A may be formed of TiN,TaN, TiAlN, TaAlN, TiSiN, or a combination thereof. The firstmetal-containing layer 126A may be formed via various vapor depositionmethods such as ALD, CVD, and PVD.

In an implementation, the second metal-containing layer 126B may beformed of an N-type metal-containing layer necessary for an NMOStransistor including an Al compound containing Ti or Ta. For example,the second metal-containing layer 126B may be formed of TiAlC, TiAlN,TiAlCN, TiAl, TaAlC, TaAlN, TaAlCN, TaAl, or a combination thereof.

In an implementation, the second metal-containing layer 126B may beformed of a P-type metal-containing layer necessary for a PMOStransistor. For example, the second metal-containing layer 126B mayinclude at least one of Mo, Pd, Ru, Pt, TiN, WN, TaN, Ir, TaC, RuN, andMoN.

The second metal-containing layer 126B may be formed of a single layeror multiple layers.

The second metal-containing layer 126B may adjust a work function of thegate structure 120, together with the first metal-containing layer 126A.A threshold voltage of the gate structure 120 may be adjusted by workfunction adjustments by the first metal-containing layer 126A and thesecond metal-containing layer 126B. According to some embodiments, thefirst metal-containing layer 126A or the second metal-containing layer126B may be omitted.

When the gate structure 120 is formed using a replacement metal gate(RMG) process, the gap-fill metal layer 128 may be formed to fill aremaining gate space on the second metal-containing layer 126B. When nogate space remains on the second metal-containing layer 126B after thesecond metal-containing layer 126B is formed, the gap-fill metal layer128 may not be formed on the second metal-containing layer 126B.

The gap-fill metal layer 128 may include, for example, W, metal nitride(e.g., TiN or TaN), Al, metal carbide, metal silicide, metal aluminumcarbide, metal aluminum nitride, or metal silicon nitride.

An integrated circuit (IC) device may include an FinFET having a3D-structure channel as illustrated in FIGS. 8A-8D. In animplementation, methods of manufacturing IC devices including planarMOSFETs may be provided via various modifications and changes.

FIGS. 9A to 9F illustrate cross-sectional views of stages in a method offabricating a semiconductor device, according to an exemplaryembodiment.

Referring to FIG. 9A, after a dummy gate electrode 120 d is formed on asubstrate 102, a spacer material layer 142 m may be conformallydeposited on the substrate 102 and an entire surface of the dummy gateelectrode 120 d.

The substrate 102 has been described above with reference to FIGS.8A-8C, and a repeated description of the substrate 102 may be omitted.

In an implementation, the dummy gate electrode 120 d may be formed of,e.g., polysilicon. The dummy gate electrode 120 d may be provided tosecure a location and a space where a gate electrode is to be formed.

The spacer material layer 142 m may include a SiOCN material layer. Inan implementation, the spacer material layer 142 m may be formed of aSiOCN single material layer. In an implementation, the spacer materiallayer 142 m may be formed of a multi-material layer in which at leasttwo materials layers including SiOCN are stacked.

A method of forming the SiOCN material layer has already been describedabove with reference to FIGS. 2-7, and thus an additional descriptionthereof may be omitted.

Referring to FIG. 9B, the spacer material layer 142 m may beanisotropically etched to form the spacers 142. The spacers 142 may beformed on sidewalls of the dummy gate electrode 120 d.

Referring to FIG. 9C, the fin-type active area FA may be partiallyremoved by using the dummy gate electrode 120 d and the spacers 142 asan etch mask.

Anisotropic etching and/or isotropic etching may be performed topartially remove the fin-type active area FA. For example, to expose atleast a portion of lower surfaces of the spacers 142, anisotropicetching and isotropic etching may be combined and thus partial etchingmay be performed.

For example, an exposed portion of the fin-type active area FA may beanisotropically etched to a predetermined depth, and then isotropicetching may be performed by wet etching. For example, an NH₄OH solution,a trimethyl ammonium hydroxide (TMAH), an HF solution, an NH₄F solution,or a mixture thereof may be used as an etchant for the wet etching.

A trench may be formed by anisotropic etching using the spacers 142 asan etch mask and may undergo the wet etching to thereby obtain a recessR via which the portions of the lower surfaces of the spacers 142 areexposed as shown in FIG. 9C. For example, the recess R may expose atleast portions of lower surfaces of the spacers that are on an impurityregion side.

In an implementation, wet etching that is performed to expose theportions of the lower surfaces of the spacers 142 may be omitted.

Then, a source/drain material layer may be formed within the recess R toform an impurity area 130. The source/drain material layer may be formedof Si, SiC, or SiGe. The source/drain material layer may be formed by,e.g., epitaxial growth. Impurities may be injected in situ duringepitaxial growth of the source/drain material layer. The impurities maybe injected via ion implantation after the source/drain material layeris formed. The impurity area 130 may have an upper surface that ishigher than an upper surface of the fin-type active area FA.

Then, the interlayer insulation layer 144 may be formed on the uppersurface of the impurity region 130. The interlayer insulation layer 144may be, e.g., silicon nitride.

Referring to FIG. 9D, the dummy gate electrode 120 d may be removed toform a gate trench GT. An upper surface of the substrate 102 may bepartially exposed via the gate trench GT. The portion of thesemiconductor substrate 102 exposed via the gate trench GT maycorrespond to a channel region of the semiconductor device that is to befabricated later.

The dummy gate electrode 120 d may be removed by, e.g., dry etching orwet etching.

Referring to FIG. 9E, the interface layer 112 may be formed. Then, ahigh-dielectric constant material layer 114 f, a first metal-containingmaterial layer 126Af, a second metal-containing material layer 126Bf,and/or a gap-fill metal material layer 128f may be sequentially formedon an upper surface of the interface layer 112, the sidewalls of thegate trench GT, and the upper surface of the interlayer insulation layer144. For example, the high-dielectric constant material layer 114 f, thefirst metal-containing material layer 126Af, and the secondmetal-containing material layer 126Bf may be conformally formed alongthe upper surface, the sidewalls, and the upper surface. The gap-fillmetal material layer 128f may be formed to fill a trench generated bythe second metal-containing material layer 126Bf.

The high-dielectric constant material layer 114 f, the firstmetal-containing material layer 126Af, the second metal-containingmaterial layer 126Bf, and the gap-fill metal material layer 128f may beindependently formed by ALD, CVD, or PVD.

Referring to FIG. 9F, a resultant structure may be planarized until theupper surface of the interlayer insulation layer 144 is exposed, therebyobtaining a final semiconductor device 100. The planarization may beperformed by, e.g., chemical mechanical polishing (CMP).

In an implementation, a source/drain region as an impurity region mayhave a raised source/drain (RSD) structure as illustrated in FIGS. 8A-8Cand FIGS. 9A-9F. In an implementation, the impurity region 130 may be animpurity-doped region formed in an area corresponding to the fin-typeactive area FA.

When a material layer forming method according to an embodiment is used,a material having a high tolerance to etching and good electriccharacteristics may be formed even at a lower temperature.

For example, a material layer having a dielectric constant of less than5.0, less than 4.8, or less than 4.4 may be fabricated even at 600° C.or less or 500° C. or less.

FIG. 10 illustrates a block diagram of an electronic device 1000according to an embodiment.

Referring to FIG. 10, the electronic device 1000 includes a logic region1010 and a memory region 1020.

The logic region 1010 may include various types of logic cells includinga plurality of circuit elements, such as a transistor and a register, asstandard cells performing desired logical functions, such as a counterand a buffer. The logic cells may constitute, for example, an AND, aNAND, an OR, a NOR, an exclusive OR (XOR), an exclusive NOR (XNOR), aninverter (INV), an adder (ADD), a buffer (BUF), a delay (DLY), a filter(FILL), a multiplexer (MXT/MXIT), an OR/AND/INVERTER (OAI), an AND/OR(AO), an AND/OR/INVERTER (AOI), a D flip-flop, a reset flip-flop, amaster-slaver flip-flop, or a latch.

The memory region 1020 may include at least one of SRAM, DRAM, MRAM,RRAM, and PRAM.

At least one of the logic region 1010 and the memory region 1020 mayinclude at least one selected from the semiconductor devices 100including the SiOCN material layer described above with reference toFIGS. 2-9E as a spacer and IC devices having various structures modifiedand changed from the semiconductor devices 100.

FIG. 11 illustrates a schematic block diagram of a display driver IC(DDI) 1500 and a display device 1520 including the DDI 1500, accordingto an embodiment.

Referring to FIG. 11, the DDI 1500 may include a controller 1502, apower supply circuit 1504, a driver block 1506, and a memory block 1508.The controller 1502 receives and decodes a command applied by a mainprocessing unit (MPU) 1522, and controls the blocks of the DDI 1500 toaccomplish an operation corresponding to the command. The power supplycircuit 1504 generates a driving voltage in response to a control of thecontroller 1502. The driver block 1506 drives a display panel 1524 byusing the driving voltage generated by the power supply circuit 1504, inresponse to a control of the controller 1502. The display panel 1524 maybe liquid crystal display panel or a plasma display panel. The memoryblock 1508 temporarily stores a command input to the controller 1502 orcontrol signals output by the controller 1502, or stores pieces ofnecessary data. The memory block 1508 may include memory such as RAM orROM. At least one of the power supply circuit 1504 and the driver block1506 may include at least one selected from the semiconductor devices100 including the SiOCN material layer described above with reference toFIGS. 2-9E as a spacer and IC devices having various structures modifiedand changed from the semiconductor devices 100.

FIG. 12 illustrates a circuit diagram of a CMOS inverter 1600 accordingto an embodiment.

The CMOS inverter 1600 includes a CMOS transistor 1610. The CMOStransistor 1610 includes a PMOS transistor 1620 and an NMOS transistor1630 connected between a power supply terminal Vdd and a groundterminal. The CMOS transistor 1610 may include at least one selectedfrom the semiconductor devices 100 including the SiOCN material layerdescribed above with reference to FIGS. 2-9E as a spacer and IC deviceshaving various structures modified and changed from the semiconductordevices 100.

FIG. 13 illustrates a circuit diagram of a CMOS SRAM 1700 according toan embodiment.

The CMOS SRAM 1700 includes a pair of driving transistors 1710. Each ofthe two driving transistors 1710 includes a PMOS transistor 1720 and anNMOS transistor 1730 connected between a power supply terminal Vdd and aground terminal. The CMOS SRAM 1700 further includes a pair oftransmission transistors 1740. Sources of the transmission transistors1740 are cross-connected to common nodes of the PMOS transistors 1720and the NMOS transistors 1730, which constitute the driving transistors1710. The power supply terminal Vdd is connected to sources of the PMOStransistors 1720, and the ground terminal is connected to sources of theNMOS transistors 1730. A word line WL is connected to gates of thetransmission transistors 1740, and a bit line BL and an inverted bitline are connected to drains of the transmission transistors 1740,respectively.

At least one of the driving transistors 1710 and the transmissiontransistors 1740 of the CMOS SRAM 1700 may include at least one selectedfrom the semiconductor devices 100 including the SiOCN material layerdescribed above with reference to FIGS. 2-9E as a spacer and IC deviceshaving various structures modified and changed from the semiconductordevices 100.

FIG. 14 illustrates a circuit diagram of a CMOS NAND circuit 1800according to an embodiment.

The CMOS NAND circuit 1800 includes a pair of CMOS transistors to whichdifferent input signals are transmitted. The CMOS NAND circuit 1800 mayinclude at least one selected from the semiconductor devices 100including the SiOCN material layer described above with reference toFIGS. 2-9E as a spacer and IC devices having various structures modifiedand changed from the semiconductor devices 100.

FIG. 15 illustrates a block diagram of an electronic system 1900according to an embodiment.

The electronic system 1900 includes a memory 1910 and a memorycontroller 1920. The memory controller 1920 controls the memory 1910 toperform data readout from and/or data writing to the memory 1910 inresponse to a request of a host 1930. At least one of the memory 1910and the memory controller 1920 may include at least one selected fromthe semiconductor devices 100 including the SiOCN material layerdescribed above with reference to FIGS. 2-9E as a spacer and IC deviceshaving various structures modified and changed from the semiconductordevices 100.

FIG. 16 illustrates a block diagram of an electronic system 2000according to an embodiment.

The electronic system 2000 includes a controller 2010, an input/output(I/O) device 2020, a memory 2030, and an interface 2040, which areconnected to one another via a bus 2050.

The controller 2010 may include at least one of a microprocessor, adigital signal processor, and a processing device that is similar tothese devices. The I/O device 2020 may include at least one of a keypad,a keyboard, and a display. The memory 2030 may store commands executedby the controller 2010. For example, the memory 2030 may store userdata.

The electronic system 2000 may form a wireless communication device, ora device capable of transmitting and/or receiving information underwireless environments. The interface 2040 may be implemented by awireless interface in order to help the electronic system 2000 totransmit/receive data via a wireless communication network. Theinterface 2040 may include an antenna and/or a wireless transceiver.According to some embodiments, the electronic system 2000 may be used ina communication interface protocol of a third-generation communicationsystem, for example, code division multiple access (CDMA), a globalsystem for mobile communications (GSM), north American digital cellular(NADC), extended-time division multiple access (E-TDMA), and/or wideband code division multiple access (WCDMA). The electronic system 2000may include at least one selected from the semiconductor devices 100including the SiOCN material layer described above with reference toFIGS. 2-9E as a spacer and IC devices having various structures modifiedand changed from the semiconductor devices 100.

By way of summation and review, when a material layer is formed at a lowtemperature, the material layer may not have desired physicalproperties. For example, when a spacer in a logic device is formed at alow temperature, electric characteristics or a physical property (e.g.,etching resistance) may not be at a desired level. Accordingly, a methodof forming a material layer having a desired physical property even at alow temperature may be desirable.

The embodiments may provide a material layer having high etchingresistance and good electric characteristics even at a low temperature.

The embodiments may provide a method of forming a SiOCN material layerhaving a high tolerance to etching and good electrical characteristics.

The embodiments may provide a material layer stack having a hightolerance to etching and good electrical characteristics.

The embodiments may provide a semiconductor device including a materiallayer stack having a high tolerance to etching and good electricalcharacteristics.

The embodiments may provide a method of fabricating a semiconductordevice including a material layer stack having a high tolerance toetching and good electrical characteristics.

The embodiments may provide a deposition apparatus capable of forming aSiOCN material layer having a high tolerance to etching and goodelectrical characteristics.

Example embodiments have been disclosed herein, and although specificterms are employed, they are used and are to be interpreted in a genericand descriptive sense only and not for purpose of limitation. In someinstances, as would be apparent to one of ordinary skill in the art asof the filing of the present application, features, characteristics,and/or elements described in connection with a particular embodiment maybe used singly or in combination with features, characteristics, and/orelements described in connection with other embodiments unless otherwisespecifically indicated. Accordingly, it will be understood by those ofskill in the art that various changes in form and details may be madewithout departing from the spirit and scope of the present invention asset forth in the following claims.

1.-48. (canceled)
 49. A method of forming a SiOCN material layer, themethod comprising: providing a substrate; providing a silicon precursoronto the substrate; providing an oxygen reactant onto the substrate;providing a first carbon precursor onto the substrate; providing asecond carbon precursor onto the substrate; and providing a nitrogenreactant onto the substrate, wherein the first carbon precursor and thesecond carbon precursor are different materials, and wherein at leastone of the first carbon precursor and the second carbon precursorincludes: an alkylamine having a carbon number of 1 to 15 or anitrogen-containing heterocyclic compound having a carbon number of 4 to15; or an alkylsilane having a carbon number of 1 to 20, an alkoxysilanehaving a carbon number of 1 to 20, or an alkylsiloxane having a carbonnumber of 1 to 20, and wherein the nitrogen reactant and the secondcarbon precursor are the same material, and providing the nitrogenreactant and providing the second carbon precursor are performedsimultaneously, and wherein the method is performed at 600° C. or less.50. The method as claimed in claim 49, wherein providing the siliconprecursor, providing the oxygen reactant, providing the first carbonprecursor, and providing the second carbon precursor are included in asingle cycle.
 51. The method as claimed in claim 49, wherein: the firstcarbon precursor includes an alkane having a carbon number of 1 to 10,an alkene having a carbon number of 2 to 10, an alkylsilane having acarbon number of 1 to 20, an alkoxysilane having a carbon number of 1 to20, or an alkylsiloxane having a carbon number of 1 to 20, and thesecond carbon precursor includes an alkylamine having a carbon number of1 to 15 or a nitrogen-containing heterocyclic compound having a carbonnumber of 4 to
 15. 52. The method as claimed in claim 51, wherein thefirst carbon precursor includes an alkylsilane having a carbon number of1 to 20, an alkoxysilane having a carbon number of 1 to 20, or analkylsiloxane having a carbon number of 1 to
 20. 53. The method asclaimed in claim 49, wherein: the silicon precursor and the first carbonprecursor include the same material, and providing the silicon precursorand providing the first carbon precursor are performed simultaneously.54. The method as claimed in claim 53, wherein providing the firstcarbon precursor, providing the oxygen reactant, and providing thesecond carbon precursor are included in a single cycle.
 55. The methodas claimed in claim 54, wherein: the first carbon precursor includes analkylsilane having a carbon number of 1 to 20, an alkoxysilane having acarbon number of 1 to 20, or an alkylsiloxane having a carbon number of1 to 20, and the second carbon precursor includes an alkylamine having acarbon number of 1 to 15 or a nitrogen-containing heterocyclic compoundhaving a carbon number of 4 to
 15. 56. The method as claimed in claim53, wherein the method is performed at 500° C. or less.
 57. A method offorming a SiOCN material layer, the method comprising: providing asubstrate; providing a silicon precursor onto the substrate; providingan oxygen reactant onto the substrate; providing a first carbonprecursor onto the substrate; providing a second carbon precursor ontothe substrate; and providing a nitrogen reactant onto the substrate,wherein the first carbon precursor and the second carbon precursor aredifferent materials, and wherein at least one of the first carbonprecursor and the second carbon precursor includes: an alkylamine havinga carbon number of 1 to 15 or a nitrogen-containing heterocycliccompound having a carbon number of 4 to 15; or an alkylsilane having acarbon number of 1 to 20, an alkoxysilane having a carbon number of 1 to20, or an alkylsiloxane having a carbon number of 1 to 20, and whereinthe silicon precursor and the second carbon precursor are the samematerial, and providing the silicon precursor and providing the secondcarbon precursor are performed simultaneously, and wherein the method isperformed at 600° C. or less.
 58. The method as claimed in claim 57,wherein providing the silicon precursor, providing the oxygen reactant,providing the first carbon precursor, and providing the nitrogenreactant are included in a single cycle.
 59. The method as claimed inclaim 57, wherein: the first carbon precursor includes an alkane havinga carbon number of 1 to 10, an alkene having a carbon number of 2 to 10,an alkylamine having a carbon number of 1 to 15, or anitrogen-containing heterocyclic compound having a carbon number of 4 to15, and the second carbon precursor includes an alkylsilane having acarbon number of 1 to 20, an alkoxysilane having a carbon number of 1 to20, or an alkylsiloxane having a carbon number of 1 to
 20. 60. Themethod as claimed in claim 59, wherein the first carbon precursorincludes an alkylamine having a carbon number of 1 to 15, or anitrogen-containing heterocyclic compound having a carbon number of 4 to15.
 61. The method as claimed in claim 57, wherein time period ofproviding a first carbon precursor onto the substrate at least partiallyoverlaps with time period of providing a second carbon precursor ontothe substrate.
 62. The method as claimed in claim 61, wherein the timeperiod of providing a first carbon precursor onto the substrate startsbefore the time period of providing a second carbon precursor onto thesubstrate starts.
 63. The method as claimed in claim 62, wherein thetime period of providing a first carbon precursor onto the substrateends after the time period of providing a second carbon precursor ontothe substrate ends.
 64. The method as claimed in claim 62, wherein thetime period of providing a first carbon precursor onto the substrateends before the time period of providing a second carbon precursor ontothe substrate ends.
 65. A method of forming a SiOCN material layer, themethod comprising: providing a substrate; providing a silicon precursoronto the substrate; providing an oxygen reactant onto the substrate;providing a first carbon precursor onto the substrate; and providing asecond carbon precursor onto the substrate; wherein the first carbonprecursor and the second carbon precursor are different materials, andwherein at least one of the first carbon precursor and the second carbonprecursor includes: an alkylamine having a carbon number of 1 to 15 or anitrogen-containing heterocyclic compound having a carbon number of 4 to15; or an alkylsilane having a carbon number of 1 to 20, an alkoxysilanehaving a carbon number of 1 to 20, or an alkylsiloxane having a carbonnumber of 1 to 20, and wherein the silicon precursor and the secondcarbon precursor are the same material, and providing the siliconprecursor and providing the second carbon precursor are performedsimultaneously, and wherein the method is performed at 600° C. or less.66. The method as claimed in claim 65, wherein: the first carbonprecursor includes an alkane having a carbon number of 1 to 10, analkene having a carbon number of 2 to 10, an alkylamine having a carbonnumber of 1 to 15, or a nitrogen-containing heterocyclic compound havinga carbon number of 4 to 15, and the second carbon precursor includes analkylsilane having a carbon number of 1 to 20, an alkoxysilane having acarbon number of 1 to 20, or an alkylsiloxane having a carbon number of1 to
 20. 67. The method as claimed in claim 66, wherein the first carbonprecursor includes an alkylamine having a carbon number of 1 to 15, or anitrogen-containing heterocyclic compound having a carbon number of 4 to15.
 68. A method of fabricating a semiconductor device, the methodcomprising: defining a fin-type active area that protrudes from asemiconductor substrate and extends in a first direction; forming a gateelectrode that covers two sidewalls and an upper surface of the fin-typeactive area, the gate electrode extending in a direction that intersectsthe first direction; forming a spacer on a sidewall of the gateelectrode; and forming impurity regions in the fin-type active arearespectively on opposite sides of the gate electrode, wherein formingthe spacer includes forming a SiOCN material layer according to claim49.